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It is reported a convenient method to obtain flame-retardant polylactic acid composite by adding low amount of crystal form II ammonium polyphosphate (APP-II) or nano-compound of crystal form II ammonium polyphosphate with calcium-based montmorillonite. The structures and thermal properties of the crystal form II ammonium polyphosphate and crystal form II ammonium polyphosphate with calcium-based montmorillonite were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. Crystallography and morphologies of the polylactic acid and its composites with the crystal form II ammonium polyphosphate and crystal form II ammonium polyphosphate with calcium-based montmorillonite were measured through differential scanning calorimeter and scanning electron microscopy. In flame retardancy of the polylactic acid composites, the 5 wt% crystal form II ammonium polyphosphate could make the polylactic acid achieve the UL-94 vertical burning V-0 rating and limited oxygen index 27.3%. When using crystal form II ammonium polyphosphate with calcium-based montmorillonite in flame-retarding polylactic acid, only 3 wt% nano-compound can result in the same V-0 rating level and the limited oxygen index of 28.0%. Meanwhile, polylactic acid with crystal form II ammonium polyphosphate or crystal form II ammonium polyphosphate with calcium-based montmorillonite still keeps the good mechanical properties. The developed systems are environmentally friendly and highly effective flame retarding, which show a promising future in practical large-scale polylactic acid application.

Al/TE (top electrode)/AlOx/Pt RRAM (resistive random access memory) devices with solution-processed spin-coated AlOx layers annealed at various temperatures (225/250/275 °C) exhibited typical bipolar resistive switching performance with low SET/RESET voltage ( 103) and excellent stability (retention time over 104 s and endurance cycles more than 100). Ni and TiN were chosen as the TE, respectively. Better RS characteristics were obtained on Ni/AlOx/Pt RRAM devices with lower operating voltage and better stability. In addition, the voltage variation between Ni/AlOx/Pt and TiN/AlOx/Pt RRAM devices was investigated. Compared with Ni/AlOx/Pt RRAM devices, TiN/AlOx/Pt devices operated with higher operation voltage at various annealing temperatures, which indicated the influence of work function difference (△ΦM) between TE and BE (bottom electrode). The greater the △ΦM, the more energy consumption and the higher operation voltage were demanded.

The components in traditional human–machine interaction (HMI) systems are relatively independent, distributed and low-integrated, and the wearing experience is poor when the system adopts wearable electronics for intelligent control. The continuous and stable operation of every part always poses challenges for energy supply. In this work, a triboelectric technology-based all-in-one self-powered HMI system for wireless remote telemetry and the control of intelligent cars is proposed. The dual-network crosslinking hydrogel was synthesized and wrapped with functional layers to fabricate a stretchable fibrous triboelectric nanogenerator (SF-TENG) and a supercapacitor (SF-SC), respectively. A self-charging power unit containing woven SF-TENGs, SF-SCs, and a power management circuit was exploited to harvest mechanical energy from the human body and provided power for the whole system. A smart glove designed with five SF-TENGs on the dorsum of five fingers acts as a gesture sensor to generate signal permutations. The signals were processed by the microcontroller and then wirelessly transmitted to the intelligent car for remote telemetry and control. This work is of paramount potential for the application of various terminal devices in self-powered HMI systems with high integration for wearable electronics.

Forest soil dissolved organic matter (DOM) is a major source of terrigenous dissolved organic carbon (DOC) that is an important component of biogeochemical cycles. While many studies have shown tha...

Microbial and emerging chemical contaminants are unwanted constituents in reclaimed wastewater, due to the health concerns of using the water for agricultural irrigation, aquifer recharges, and potable water. Removal of these contaminants is required but it is currently challenging, given that there is no simple treatment technology to effectively remove the mixture of these contaminants. This study examined the effectiveness of ZnO-assisted photocatalytic degradation of several constituents, including 1,4-dioxane, trihalomethanes (THMs), triclosan (TCS), triclocarban (TCC), antibiotic resistant bacteria (ARB) and antibiotic resistant genes (ARGs), under low intensity of UV exposure. E. coli with an ARGs-carrying circular plasmid (pUC19) was used as a model antibiotic resistant bacterium. Our results show that commercial zinc oxide (C-ZnO) assisted photodegradation of 1,4-dioxane, and dehalogenation of THMs, TCS, and TCC, while tetrapodal zinc oxide (T-ZnO) enhanced the dehalogenation of TCS and TCC. Additionally, T-ZnO assisted the photocatalytic inactivation of the E. coli within 6 h and caused structural changes in the plasmid DNA (pUC19) with additional UV exposure, resulting in non-functional AGR-containing plasmids. These results also suggest that higher UV dose is required not only to inactivate ARB but also to damage ARGs in the ARB in order to decrease risks in promoting ARB population in the environment. Overall, our results implicated that, under low UV intensity, ZnO-assisted photocatalysis is a promising alternative to simultaneously remove biological and emerging chemical contaminants in treated wastewater for safe reuse.

Self-healable soft conductors, which can withstand certain degrees of deformation and can recover from damage spontaneously, are essential for wearable applications. In this work, a soft hydrogel based self-healing triboelectric nanogenerator (HS-TENG), which is highly deformable, and both mechanically and electrically self-healable, has been successfully fabricated from a poly(vinyl alcohol)/agarose hydrogel. The incorporation of photothermally active polydopamine particles and multiwalled carbon nanotubes (MWCNTs) allows the HS-TENG to be physically self-healed in ∼1 min upon exposure to near-infrared (NIR) light. At the same time, the chemical self-healing of the HS-TENG can be triggered by water spraying at 25 °C when introducing water-active dynamic borate bonds into the hydrogel. The applicability of the HS-TENG as a soft energy device to harvest human motion energies has been demonstrated. By tapping the HS-TENG with various deformations, the rectified electricity can charge commercial LEDs with sustainable energy. Working in single-electrode mode, the electrical outputs of the HS-TENG in terms of short-circuit transferred charge (Qsc), open circuit voltage (Voc) and short-circuit current (Isc) reach ∼32 nC, ∼95 V and ∼1.5 μA, respectively, and remain stable even with 200% strain since the MWCNTs disperse evenly in the matrix and play the role of conductive fillers in the HS-TENG.

In this work, oxide resistive random access memory (OxRRAM) devices with stacked solution-processed (SP) metal oxide (MO) layers were fabricated to investigate artificial synaptic behavior such as long-term potentiation (LTP) and long-term depression (LTD). The stacked RRAM devices exhibited stable and repeated bipolar IV curves with operation voltage lower than the ~0.5 V and a switching ratio larger than 2*104. Also, with the stimuli from external consecutive pulses, the stacked devices demonstrated learning-forgetting-relearning behavior similar to neuron-induced behavior in the human brain. Finally, based on stable long-term memory performance, the pattern recognition system with an artificial neuron network (ANN) algorithm was simulated with the recognition accuracy higher than 95%.

Hurricane Harvey led to a broad redistribution of sediment throughout Galveston Bay and the Houston Ship Channel (GB/HSC), but the resulting changes in chemical contaminant distributions have yet to be characterized. To address this question, we collected and analyzed post-Harvey sediment for concentrations of the EPA 16 Priority Pollutant polycyclic aromatic hydrocarbon (PAHs), determining the extent to which the spatial distribution and sourcing of contaminants may have changed in contrast to historical surface sediment data (5 cm) from the National Oceanic Atmospheric Administration (NOAA) available for the years 1996-2011. We found a small, but detectable increase from pre- to post-Harvey in PAH concentrations, with PAH diagnostic sourcing indicating combustion origins. Of the detected PAHs, none exceeded Sediment Quality Guideline values. Overall, we have added to the understanding of PAH spatial trends within the GB/HSC region, and developed a reference PAH baseline to inform future studies.

Copper-based algaecides are usually used for controlling algae bloom triggered by the elevated levels of nutrients after wildfires, resulting in the promoted reactivity of dissolved organic matter (DOM) in forming disinfectant byproducts (DBPs). To identify the best strategy for handling this source water, we employed Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to characterize the DBPs precursors after 4-d Microcystis aeruginosa bloom cultured with black (BE) and white (WE) ash water extracts under 0, 0.5, and 1.0 mg-Cu/L. The disappeared DOM during disinfections, primarily composed of O1-14, N1O1-14 and N2O1-14, had a higher average molecular weight (MW) and double-bond equivalent (DBE), relative to DOM after incubation, regardless of disinfects and Cu2+. This result suggests assigned features with larger MW and more double bonds/rings as preferable DBP precursors. We observed a larger number of disappeared assigned features with low DBE of 1-10 in control without Cu2+ addition, possibly explaining lower DOM chlorine reactivity in forming carbonaceous and oxygenated DBPs, relative to the treatments with Cu2+ addition. We found a larger number of O1-14 and N1O1-14 with DBE=5-16 in the treatments, potentially explaining higher DOM chloramine reactivity in forming N-nitrosodimethylamine (NDMA), compared to the control. Our study suggests removing oxygen- and nitrogen-containing organic compounds with more double bonds/aromatic rings as a preferable strategy for handling source water after controlling post-fire algae blooms with copper sulfate.

Here, we examine how marine microbial communities respond when dissolved organic matter (DOM) is mobilized from coastal wetlands. Biological transformations of this DOM may increase in the presence of reactive substrates, such as algal‐derived DOM (ADOM) in the coastal zone—a process known as priming. We performed laboratory experiments examining transformations of DOM derived from coastal wetland peat (PDOM) with and without the presence ADOM. Associated shifts in microbial community composition and functional gene abundance were measured to evaluate mechanisms of priming effects. ADOM presence stimulated CO2 production when compared to the seawater control, which was further enhanced in the copresence of PDOM. DOM characterization showed a substantial difference in features present at the end of the incubation when PDOM was present with and without ADOM, while metagenomic sequencing indicated shifts in microbial community composition and identified 23 unique functional genes associated with pathways for the breakdown of aromatic compounds.

Per- and poly-fluoroalkyl substances (PFASs) are man-made chemicals that are toxic and widely detected in the environment, including drinking water sources. A cost-effective treatment process for PFASs is currently not available. We developed reusable hydrogel sorbents to remove long- and short-chain perfluoroalkyl acids and 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoic acid (GenX), which is are emerging PFAS. Through fluoridation and amination of poly(ethylene glycol) diacrylate (PEGDA), the newly synthesized sorbents can sorb the five targeted PFASs (perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorobutanesulfonic acid (PFBS), and perfluorobutanoic acid (PFBA) and GenX) to different degrees from aqueous solution. Aminated PEGDA showed the highest sorption capacity for all five PFASs, particularly for PFBA and PFBS. The bifunctionalized PEGDA showed higher capacities for PFOA and PFOS, suggesting that both hydrophobic interactions and charges contribute to the sorption. Both aminated and bifunctionalized sorbents can remove GenX from water, with the highest sorption capacity of 98.7 μmol g aminated PEGDA–1 within 6 h. The absorbed PFASs on the sorbents were observed and characterized by Fourier-transform infrared spectroscopy. The spent sorbents were reusable after readily regenerated with 70% methanol contained 1% NaCl.

2,3,3,3-Tetrafluoro-2-(heptafluoropropoxy)propanoate (known as GenX) has been used as an alternative to perfluorooctanoic acid (PFOA) which was phased out of formulations for industrial and consumer product applications in 2015. While the effects of GenX on lab animals have been studied, little is known about its effects on plants. This study examined and compared the accumulation and toxicity of GenX and PFOA in the model plants Arabidopsis thaliana and Nicotiana benthamiana. Both plants showed reduction in biomass and root growth following exposure to PFOA or GenX in a dosage-dependent manner. The bioaccumulation factors (BFs) of GenX and PFOA were plant species-dependent, with higher BFs in A. thaliana compared to N. bethanminana. Additionally, GenX and PFOA were more readily accumulated into shoot tissues of A. thaliana than in N. bethanminana. Exposure to GenX also caused a reduction in chlorophyll content (18%) and total phenolic compounds (26%). However, GenX exposure increased superoxide dismutase activity and H2O2 content (1.6 and 2.6 folds increase, respectively) in N. benthamiana. Overall, our result suggest that GenX is bioaccumulative, and that its accumulation likely inhibits plant growth and photosynthesis as well as inducing oxidative stress.

Kidney is a major route of xenobiotic excretion, but the accuracy of preclinical data for predicting in vivo clearance is limited by species differences and non-physiologic 2D culture conditions. Microphysiological systems can potentially increase predictive accuracy due to their more realistic 3D environment and incorporation of dynamic flow. We used a renal proximal tubule microphysiological device to predict renal reabsorption of five compounds: creatinine (negative control), perfluorooctanoic acid (positive control), cisplatin, gentamicin, and cadmium. We perfused compound-containing media to determine renal uptake/reabsorption, adjusted for non-specific binding. A physiologically-based parallel tube model was used to model reabsorption kinetics and make predictions of overall in vivo renal clearance. For all compounds tested, the kidney tubule chip combined with physiologically-based modeling reproduces qualitatively and quantitatively in vivo tubular reabsorption and clearance. However, because the in vitro device lacks filtration and tubular secretion components, additional information on protein binding and the importance of secretory transport is needed in order to make accurate predictions. These and other limitations, such as the presence of non-physiological compounds such as antibiotics and bovine serum albumin in media and the need to better characterize degree of expression of important transporters, highlight some of the challenges with using microphysiological devices to predict in vivo pharmacokinetics.

A suite of biomarkers, including amino acids, pigments, and lignin phenols coupled with high resolution mass spectrometry were used to evaluate differences in the sources and fate of organic matter (OM) in Everglades treatment wetlands as a model for OM cycling in shallow water wetlands. Five components of the system (water column particulate matter, vertical traps, flocculent material, periphyton, and surface soil) were assessed for OM transformations down-profile (i.e. water column to soil) and between treatment cells dominated by emergent aquatic vegetation (EAV) and submerged aquatic vegetation (SAV), with comparisons to reference sites within the remnant Everglades. We found that OM cycling is fundamentally different between EAV and SAV wetlands, and that SAV wetlands have some shared characteristics with similar habitats in the remnant Everglades. Other than locations densely populated by Typha spp., water column particulate organic C was predominantly derived from microbial/cryptomonad sources, rather than macroscopic sources (vascular plants and algal mats). Bacterial amino acid biomarkers were positively correlated with amino acid degradation indices and organic P (Po), respectively suggesting that microbial abundance is associated with less degraded OM, and that further investigation into relationships between microbial biomass and Po is warranted. Overall, this multi-biomarker approach can elucidate the relative degradation of OM pools, identify sources of OM, and highlight the importance of water column processes in shallow water wetlands.

The rapid development of wearable electronics has led to an enormous demand for power sources that are wearable, small-scale, flexible and compatible. In this work, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as the liquid electrode and silicone rubber as the triboelectric/encapsulation layer were introduced to design a stretchable PEDOT:PSS liquid electrode-based triboelectric nanogenerator (PL-TENG). The elastic silicone rubber and PEDOT:PSS liquid electrode with a special macromolecular structure endowed PL-TENG with extraordinary flexibility and conductivity simultaneously. Working under the single-electrode mode with different motion frequencies from 0.5 to 2.5 Hz, PL-TENG generated open-circuit voltage of 265 V, short-circuit current of 24.9 μA and short-circuit charge quantity of 85 nC. The output performances still maintained the original values after washing in saline, storing for one month and stretching 10 000 times. At the same time, PL-TENG could also produce stable electrical outputs even when deformed into a variety of shapes including stretching in different directions, bending and twisting. All of these features demonstrated the excellent resistance of PL-TENG to sweat, time and deformation. When attached to a human body, PL-TENG could provide a sufficiently stable power output to drive wearable electronics sustainably.

Per- and poly-fluorinated alkyl substances (PFAS) are a group of highly persistent synthetic chemicals utilized in many industrial and consumer products, and — significantly toward introduction to the marine environment — in fire-fighting foams. Recently, PFAS have been linked to adverse health effects, prompting the need to better understand transport, lability, and fate. Perfluorooctanesulfonic acid (PFOS), a manufactured PFAS and biodegradation product, partitions to marine sediments and thus can be used as a primary indicator toward regulatory efforts. The current study offers a spatial and temporal analysis of Puget Sound from cores collected adjacent Tacoma and Seattle, WA, as well as cores from central Hood Canal and Carr Inlet. Temporal fluxes reflected releases into the environment corresponding with initial production and subsequent increases in use. Biologically active layers ranged from 434 pg/g (Carr Inlet) to 824 pg/g (Hood Canal) PFOS, producing benthic community risk quotients between 0.11 and 0.17.

Triboelectric nanogenerator (TENG) has shown great advances in converting low-frequency discrete mechanical energy into electricity and multifunctional real-time self-powered sensing systems. It has confirmed that the air breakdown effect is the main factor limiting the maximum effective power output of the TENG. Charges generated on the surface of TENGs diffuse into the atmosphere and internal triboelectric layer, resulting in charge loss and decrease of surface charge density. Breaking through the limitation of air breakdown and prolonging charge decay time are the two priorities for boosting TENG output. By embedding superior intermediate layer into TENG induced output enhancement provides an effective strategy to improve the output performance. Here, the working mechanisms of different materials belonging to the classifications of metals, inorganic non-metal materials, and organic polymers as the intermediate layer are reviewed elaborately. Moreover, the influences of structure parameters, such as thickness of dielectric layer, dielectric layer number, and ground connection design are discussed accordingly. Future challenges and optimizations for improvement of the intermediate layer are finally presented in the review.

Extensive undersaturations of carbon tetrachloride (CCl4) in Pacific, Atlantic, and Southern Ocean surface waters indicate that atmospheric CCl4 is consumed in large amounts by the ocean. Observations made on 16 research cruises between 1987 and 2010, ranging in latitude from 60° N to 77° S, show that negative saturations extend over most of the surface ocean. Corrected for physical effects associated with radiative heat flux, mixing, and air injection, these anomalies were commonly on the order of −5 to −10 %, with no clear relationship to temperature, productivity, or other gross surface water characteristics other than being more negative in association with upwelling. The atmospheric flux required to sustain these undersaturations is 12.4 (9.4–15.4) Gg yr−1, a loss rate implying a partial atmospheric lifetime with respect to the oceanic loss of 183 (147–241) yr and that ∼ 18 (14–22) % of atmospheric CCl4 is lost to the ocean. Although CCl4 hydrolyzes in seawater, published hydrolysis rates for this gas are too slow to support such large undersaturations, given our current understanding of air–sea gas exchange rates. The even larger undersaturations in intermediate depth waters associated with reduced oxygen levels, observed in this study and by other investigators, strongly suggest that CCl4 is ubiquitously consumed at mid-depth, presumably by microbiota. Although this subsurface sink creates a gradient that drives a downward flux of CCl4, the gradient alone is not sufficient to explain the observed surface undersaturations. Since known chemical losses are likewise insufficient to sustain the observed undersaturations, this suggests a possible biological sink for CCl4 in surface or near-surface waters of the ocean. The total atmospheric lifetime for CCl4, based on these results and the most recent studies of soil uptake and loss in the stratosphere is now 32 (26–43) yr.

Background Endothelial barrier dysfunction is central to the pathogenesis of sepsis-associated acute lung injury (ALI). Microtubule (MT) dynamics in vascular endothelium are crucial for the regulation of endothelial barrier function. Unfractionated heparin (UFH) possesses various biological activities, such as anti-inflammatory activity and endothelial barrier protection during sepsis. Methods Here, we investigated the effects and underlying mechanisms of UFH on lipopolysaccharide (LPS)-induced endothelial barrier dysfunction. C57BL/6 J mice were randomized into vehicle, UFH, LPS and LPS + UFH groups. Intraperitoneal injection of 30 mg/kg LPS was used to induce sepsis. Mice in the LPS + UFH group received intravenous UFH 0.5 h prior to LPS injection. Human pulmonary microvascular endothelial cells (HPMECs) were cultured for analyzing the effects of UFH on LPS-induced and nocodazole-induced hyperpermeability, F-actin remodeling, and LPS-induced p38 MAPK activation. Results UFH pretreatment significantly attenuated LPS-induced pulmonary histopathological changes, and increased the lung W/D ratio and Evans blue accumulation in vivo. Both in vivo and in vitro studies showed that UFH pretreatment blocked the LPS-induced increase in guanine nucleotide exchange factor (GEF-H1) expression and myosin phosphatase target subunit 1 (MYPT1) phosphorylation, and microtubule (MT) disassembly in LPS-induced ALI mouse model and human pulmonary microvascular endothelial cells (HPMECs). These results suggested that UFH ameliorated LPS-induced endothelial barrier dysfunction by inhibiting MT disassembly and GEF-H1 expression. In addition, UFH attenuated LPS-induced hyperpermeability of HPMECs and F-actin remodeling. In vitro, UFH pretreatment inhibited LPS-induced increase in monomeric tubulin expression and decrease in tubulin polymerization and acetylation. Meanwhile, UFH ameliorates nocodazole-induced MTs disassembly and endothelial barrier dysfunction.Additionally, UFH decreased p38 phosphorylation and activation, which was similar to the effect of the p38 MAPK inhibitor, SB203580. Conclusions UFH exert its protective effects on pulmonary microvascular endothelial barrier dysfunction via microtubule stabilization and is associated with the p38 MAPK pathway.

Knowledge of dynamic interactions between natural organic matter (NOM) and microbial communities is critical not only to delineate the routes of NOM degradation/transformation and carbon (C) fluxes, but also to understand microbial community evolution and succession in ecosystems. Yet, these processes in subsurface environments are usually studied independently, and a comprehensive view has been elusive thus far. In this study, we fed sediment-derived dissolved organic matter (DOM) to groundwater microbes and continually analyzed microbial transformation of DOM over a 50-day incubation. To document fine-scale changes in DOM chemistry, we applied high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and soft X-ray absorption spectroscopy (sXAS). We also monitored the trajectory of microbial biomass, community structure and activity over this time period. Together, these analyses provided an unprecedented comprehensive view of interactions between sediment-derived DOM and indigenous subsurface groundwater microbes. Microbial decomposition of labile C in DOM was immediately evident from biomass increase and total organic carbon (TOC) decrease. The change of microbial composition was closely related to DOM turnover: microbial community in early stages of incubation was influenced by relatively labile tannin- and protein-like compounds; while in later stages the community composition evolved to be most correlated with less labile lipid- and lignin-like compounds. These changes in microbial community structure and function, coupled with the contribution of microbial products to DOM pool affected the further transformation of DOM, culminating in stark changes to DOM composition over time. Our study demonstrates a distinct response of microbial communities to biotransformation of DOM, which improves our understanding of coupled interactions between sediment-derived DOM, microbial processes, and community structure in subsurface groundwater.

Brominated very short-lived substances (BrVSLS), such as bromoform, are important trace gases for stratospheric ozone chemistry. These naturally derived trace gases are formed via bromoperoxidase-mediated halogenation of dissolved organic matter (DOM) in seawater. Information on DOM type in relation to the observed BrVSLS concentrations in seawater, however, is scarce. We examined the sensitivity of BrVSLS production in relation to the presence of specific DOM moieties. A total of 28 model DOM compounds in artificial seawater were treated with vanadium bromoperoxidase (V-BrPO). Our results show a clear dependence of BrVSLS production on DOM type. In general, molecules that comprise a large fraction of the bulk DOM pool did not noticeably affect BrVSLS production. Only specific cell metabolites and humic acid appeared to significantly enhance BrVSLS production. Amino acids and lignin phenols suppressed enzyme-mediated BrVSLS production and may instead have formed halogenated nonvolatile molecules. Dibromomethane production was not observed in any experiments, suggesting it is not produced by the same pathway as the other BrVSLS. Our results suggest that regional differences in DOM composition may explain the observed BrVSLS concentration variability in the global ocean. Ultimately, BrVSLS production and concentrations are likely affected by DOM composition, reactivity, and cycling in the ocean.

Unfractionated heparin (UFH) is largely used as anti-thrombotic drug. While UFH has been shown to suppress lipopolysaccharide (LPS)-induced nuclear factor-κB (NF-κB) activation, intracellular upstream events that cause NF-κB down-regulation in response to UFH remain unclear. Thus, we investigated the involvement of phosphoinositide-3-OH kinase (PI3K)/Akt in the inhibition of LPS-activated NF-κB pathway by UFH in human pulmonary microvascular endothelial cells (HPMECs). Pretreatment with UFH (0.1-1U/ml) significantly inhibited LPS (10μg/ml)-stimulated interleukin (IL)-6 and IL-8 production in HPMECs. LPS activated Akt and NF-κB, whereas UFH suppresses LPS-induced Akt phosphorylation and NF-κB nuclear translocation, which were required for IL-6 and IL-8 gene transcription. Inhibition studies by using wortmannin abrogated NF-κB-mediated IL-6 and IL-8 expression, suggesting the requirement of PI3K/Akt pathway. Our data provided the first evidence that UFH might repress LPS-activated PI3K/Akt pathway, leading to inhibitory effect of NF-κB activation with diminished IL-6 and IL-8 expression in HPMECs.

Ultrahigh resolution mass spectrometry, such as Fourier transform ion cyclotron resonance mass spectrometry (FT ICR MS), can resolve thousands of molecular ions in complex organic matrices. A Compound Identification Algorithm (CIA) was previously developed for automated elemental formula assignment for natural organic matter (NOM). In this work, we describe software Formularity with a user-friendly interface for CIA function and newly developed search function Isotopic Pattern Algorithm (IPA). While CIA assigns elemental formulas for compounds containing C, H, O, N, S, and P, IPA is capable of assigning formulas for compounds containing other elements. We used halogenated organic compounds (HOC), a chemical class that is ubiquitous in nature as well as anthropogenic systems, as an example to demonstrate the capability of Formularity with IPA. A HOC standard mix was used to evaluate the identification confidence of IPA. Tap water and HOC spike in Suwannee River NOM were used to assess HOC identification in complex environmental samples. Strategies for reconciliation of CIA and IPA assignments were discussed. Software and sample databases with documentation are freely available.

[1] Atmospheric mixing ratios and seawater concentrations of bromoform (CHBr3), dibromomethane (CH2Br2), and other brominated very short-lived substances (BrVSLS) were measured during five cruises from 1994 to 2010. These cruises were conducted over large latitudinal (62°N–60°S) and longitudinal transects (11°W–86°W) in the Atlantic Ocean. Elevated seawater concentrations of CHBr3 and CH2Br2 were often observed in regions where chlorophyll a concentrations were also elevated, which suggests biogeochemical processes associated with photosynthetic biomass may be related to CHBr3 and CH2Br2 production. Our results suggest that, at least in the open ocean, several phytoplankton taxa may contribute to the production of these trace gases. While observed correlations between CHBr3 and CH2Br2 in different regions are usually interpreted as common sources for these compounds, results in this study suggest different biogeochemical processes may contribute separately to the production of these trace gases. Heterotrophic bacterial abundance was significantly correlated with CH2Br2, but not with CHBr3, which suggests the biogeochemical processes associated with heterotrophic bacteria may be related to CH2Br2 in seawater but probably not to CHBr3. In general, the Atlantic Ocean is a net source for CHBr3 and CH2Br2, except for a few locations where these trace gases were undersaturated in seawater. Assuming fluxes measured in the Atlantic open ocean are globally representative, the resulting extrapolated, global open-ocean annual net sea-to-air fluxes calculated from data from the five cruises was estimated at 0.24–3.80 Gmol Br yr−1 for CHBr3 and 0.11–0.77 Gmol Br yr−1 for CH2Br2.

[1] Seawater concentrations and distributions of brominated very short-lived substances (BrVSLS), including bromoform (CHBr3), dibromomethane (CH2Br2), bromodichloromethane (CHBrCl2), chlorodibromomethane (CHClBr2), were measured in the upper water column (5–750 m) in the eastern Pacific. Inorganic nutrient, pigment concentrations, and picoplankton cell counts were measured to determine biogeochemical factors that affect the production and distribution of these BrVSLS. Elevated concentrations of BrVSLS were observed in coastal and tropical seawater. Concentration maxima for CHBr3, CH2Br2, and CHClBr2 were observed below the mixed layer, near the subsurface chlorophyll a maxima, which suggest BrVSLS production may be related to photosynthetic biomass production. Our results also suggest that heterotrophic bacteria may also contribute to CH2Br2 and CHBrCl2 production in the water column. The maximum CHBrCl2 concentration was observed at a depth much deeper than the euphotic zone, which suggests sources other than photosynthetic biomass. Elevated CHBrCl2 concentrations in deeper waters were coincident with elevated CHCl3 concentrations, which may be an evidence for successive chlorine substitution of CHBr3 in deeper and older water masses.

Unfractionated heparin (UFH) and low-molecular-weight heparins (LMWH), apart from anticoagulant activities, contain a variety of biological properties such as anti-inflammatory actions possibly affecting sepsis. Chemokines are vital for promoting the movement of circulating leukocytes to the site of infection and are involved in the pathogenesis of sepsis. The purpose of this study was to investigate the effects and potential mechanisms of UFH on lipopolysaccharide (LPS)-induced chemokine production in human pulmonary microvascular endothelial cells (HPMECs). HPMECs were pretreated with UFH (0.1 U/ml and 1 U/ml), 15 min prior to stimulation with LPS (10 μg/ml). Cells were cultured under various experimental conditions for 2 h and 6 h for analysis. UFH markedly decreased LPS-induced interleukin (IL)-8 and monocyte chemoattractant protein-1 (MCP-1) mRNA and protein expression in HPMECs. UFH also attenuated the secretion of these chemokines in culture supernatants. In addition, UFH blocked the chemotactic activities of LPS-stimulated HPMECs supernatants on monocytes migration as expected. UFH inhibited LPS-induced Kruppel-like factor 5 (KLF-5) mRNA and protein levels. Concurrently, UFH reduced nuclear factor (NF)-κB nuclear translocation. Importantly, transfection with siRNA targeting KLF-5 reduced NF-κB activation and chemokines expression. These results demonstrate that interfering with KLF-5 mediated NF-κB activation might contribute to the inhibitory effects of chemokines and monocytes migration by UFH in LPS-stimulated HPMECs.

The present study aimed to determine the protective effects and the underlying mechanisms of unfractionated heparin on lipopolysaccharide (LPS)-induced endotoxemia and lung injury in rats. Rats were injected intravenously with LPS at 6 mg/kg. We examined the therapeutic effects of unfractionated heparin (100 or 300 U/kg) on LPS-induced endotoxemia by dosing intravenously simultaneously after LPS challenge. The animal lung edema degree was evaluated by wet/dry weight ratio. The levels of inflammatory mediators including interleukin-1β (IL-1β) and interleukin-6 (IL-6) were assayed by enzyme-linked immunosorbent assay and quantitative real-time RT-PCR. The activation of nuclear factor-κB (NF-κB) was evaluated by Western blotting. The investigations revealed that treatment with unfractionated heparin can attenuate inflammatory responses in a rat model of LPS-induced acute lung injury, and the effect was much better in 300 U/kg group. The mechanisms by which unfractionated heparin exerts its anti-inflammatory effect are correlated with inhibition of IL-1β and IL-6 production via inactivation of NF-κB.

[1] Saturation-anomaly measurements of methyl bromide (CH3Br) were made in the eastern Pacific (3/30–4/27, 2010) and the eastern Atlantic (10/25–11/26, 2010) to assess the oceanic saturation state as the phaseout of fumigation - non-Quarantine and Pre-Shipment (non-QPS) uses of CH3Br nears completion and atmospheric concentrations continue to decline. These cruises occurred 16 years after the Bromine Latitudinal Air-Sea Transect (BLAST) cruises, which were conducted in the same regions and first established a global oceanic net sink of −12.6 Gg yr−1 for atmospheric CH3Br in 1994. Results from this study suggest saturation anomalies of CH3Br in the surface ocean have become less negative than those observed 16 years ago as the atmospheric burden has declined over the past decade. The global net sea-to-air flux was estimated at 0 to 3 Gg yr−1 in 2010, suggesting that the ocean may become a net small source to atmospheric CH3Br. There are no significant differences between this study and previous studies for measured biological loss rate constants and calculated annual production rates, suggesting that annual production rates and biological degradation rate constants for CH3Br in the surface ocean have likely remained relatively constant over the past 16 years. When including the biological loss rate constants from this study and all previous studies, the mean global biological loss rate constant is constrained to 0.05 ± 0.01 d−1 (at a 95% confidence level). Combining chemical and eddy degradation rate constants, and using an updated gas transfer velocity, we estimate the CH3Br partial atmospheric lifetime with respect to oceanic loss to be 3.1 (2.3 to 5.0) years. Although the new partial atmospheric lifetime is about 1.3 years longer than the best prior estimate, it does not change the overall atmospheric lifetime of CH3Br, 0.8 (0.7–0.9) years.

Mahajan, A. S. ... et. al.-- 9 pages, 6 figures, supplementary material related to this article is available online at: http://www.atmos-chem-phys.net/12/11609/2012/acp-12-11609-2012-supplement.pdf, Ship-based Multi-Axis Differential Optical Absorption Spectroscopy measurements of iodine monoxide (IO) and atmospheric and seawater Gas Chromatography-Mass Spectrometer observations of methyl iodide (CH3I) were made in the Eastern Pacific marine boundary layer during April 2010 as a part of the HaloCarbon Air Sea Transect-Pacific (HaloCAST-P) scientific cruise. The presence of IO in the open ocean environment was confirmed, with a maximum differential slant column density of 5 × 1013 molecules cm -2 along the 1 elevation angle (corresponding to approximately 1 pptv) measured in the oligotrophic region of the Southeastern Pacific. Such low IO mixing ratios and their observed geographical distribution are inconsistent with satellite estimates and with previous understanding of oceanic sources of iodine. A strong correlation was observed between reactive iodine (defined as IO + I) and CH3I, suggesting common sources. In situ measurements of meteorological parameters and physical ocean variables, along with satellite-based observations of Chlorophyll a(Chl a) and Chromophoric Dissolved Organic Matter (CDOM) were used to gain insight into the possible sources of iodine in this remote environment. Surprisingly, reactive iodine showed a negative correlation (> 99% confidence) to Chl a and CDOM across the cruise transect. However, a significant positive correlation (> 99% confidence) with sea surface temperature (SST) and salinity instead suggests a widespread abiotic source related to the availability of aqueous iodine and to temperature. © Author(s) 2012. CC Attribution 3.0 License, The Spanish Research Council and the Regional Government of Castilla-La Mancha funded this work. S. Yvon-Lewis acknowledges funding from the National Science Foundation (NSF/OCE 0927874) supporting the shiptime and the halocarbon measurements

OBJECTIVE: To establish the chromatographic fingerprints for the anti-tumor flavonoids of Caulis spatholobi (SSCE). It could used to reflect the chemical information in this part comprehensively, and identify the chemical consitituents preliminarily. METHOD: The HPLC-DAD analysis method was performed on the column Kromasil 100-5PHENYL (4.6 mm x 250 mm, 5 microm). The mobile phase was water (0.5% acetic acid)- methanol in gradient elution and the detection wavelength was 254 nm. RESULT: The chromatographic fingerprint of SSCE was established, which showed 16 characteristic peaks from 10 batches of medicinal materials. Among them, the peaks 1, 3, 4, 5, 8, 9, 10, 12, 13, and 16 were identified 3,4-dihodroxybenzoic acid, 4-Hydroxybenzoic Acid, epicatechin, puerarin, daidzein, liquiritigenin, calycosin, genistein, formononetin, and prunetin, respectively. CONCLUSION: The method is convenient, reproducibility and stability. It can used for quality control of the anti-tumor flavonoids of C. spatholobi (SSCE).

[1] Brominated very short-lived substances (VSLSs) such as bromoform (CHBr3), dibromomethane (CH2Br2), and chlorodibromomethane (CHClBr2) are receiving increasing attention, due to their important role in tropospheric and lower stratospheric ozone (O3) chemistry. These brominated VSLSs were measured in air and surface water during the Gulf of Mexico and East Coast Carbon (GOMECC) cruise in the summer of 2007. Mean atmospheric mixing ratios for CHBr3, CH2Br2 and CHClBr2 for the entire cruise were 14.6 (0.7 to 138.3) ppt, 2.8 (0.5 to 13.2) ppt, and 0.5 (0.03 to 3.2) ppt, respectively; and mean sea-surface water concentrations were 66.0 (4.4 to 1724.8) pmol L−1, 10.6 (1.9 to 153.8) pmol L−1, and 1.0 (0.1 to 17.2) pmol L−1, respectively. These compounds were supersaturated almost everywhere in the study region, except a few locations in the Florida Straits and along the east coast of Florida, where negative saturation anomalies and fluxes were observed. Mean net fluxes observed during the GOMECC cruise for CHBr3, CH2Br2, and CHClBr2 were 47.6 (−25.4 to 1056.3) nmol m−2 d−1, 9.7 (−0.5 to 112.3) nmol m−2 d−1, and 0.8 (−1.2 to 10.8) nmol m−2 d−1, respectively. The net fluxes for these polybrominated compounds from the coastally influenced waters (bottom depth ≤200 m) are significantly higher than the net fluxes observed in the open ocean (bottom depth >200 m).

[1] Measurements of methyl bromide (CH3Br) and methyl chloride (CH3Cl) were made during the Gulf of Mexico and the East Coast Carbon (GOMECC) cruise in the summer of 2007. This was the first large-scale study of CH3Br and CH3Cl in the coastal ocean. The mean atmospheric mixing ratios were 10.1 ppt for CH3Br and 517 ppt for CH3Cl. Surface seawater concentrations ranged from 0.8 pM to 5.0 pM for CH3Br and from 61.5 pM to 179 pM for CH3Cl. Biological processes contribute to the elevated seawater concentrations of CH3Br, while a combination of biological processes and terrestrial sources may contribute to elevated seawater concentrations of CH3Cl. Vertical distributions show highest concentrations of CH3Br and CH3Cl in the subsurface seawater below the mixed layer due to high degradation rates near the surface. Good correlation of the production rates between CH3Br and CH3Cl suggests they have some common sources in the coastal ocean. After excluding the open ocean points, annual coastal emissions in the studied region were 0.01–0.06 Gg yr−1 for CH3Br and 0.3–1.6 Gg yr−1 for CH3Cl. By simple extrapolation, the global coastal emissions were estimated at 0.5–3.6 Gg yr−1 for CH3Br and 19–98 Gg yr−1 for CH3Cl. Including the coastal ocean emissions of CH3Br and CH3Cl will increase the estimate of global oceanic emissions by 1%–9% and 1%–8%, respectively.

Polar petroleum components enter marine environments through oil spills and natural seepages each year. Lately, they are receiving increased attention due to their potential toxicity to marine organisms and persistence in the environment. We conducted a laboratory experiment and employed state-of-the-art Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to characterize the polar petroleum components within two operationally-defined seawater fractions: the water-soluble fraction (WSF), which includes only water-soluble molecules, and the water-accommodated fraction (WAF), which includes WSF and microscopic oil droplets. Our results show that compounds with higher heteroatom (N, S, O) to carbon ratios (NSO:C) than the parent oil were selectively partitioned into seawater in both fractions, reflecting the influence of polarity on aqueous solubility. WAF and WSF were compositionally distinct, with unique distributions of compounds across a range of hydrophobicity. These compositional differences will likely result in disparate impacts on environmental health and organismal toxicity, and thus highlight the need to distinguish between these often-interchangeable terminologies in toxicology studies. We use an empirical model to estimate hydrophobicity character for individual molecules within these complex mixtures and provide an estimate of the potential environmental impacts of different crude oil components.